In contrast to a recently expressed, and widely cited, view that “Ionic liquids are starting to leave academic labs and find their way into a wide variety of industrial applications”, we demonstrate in this critical review that there have been parallel and collaborative exchanges between academic research and industrial developments since the materials were first reported in 1914 (148 references)

Applications of ionic liquids in the chemical industry

2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628

Catalysis in ionic liquids

ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

Structure and nanostructure in ionic liquids.

2.7. Hydroxylation Reactions of Allenes 3282 2.8. Hydroamination Reactions of Allenes 3284 2.9. Hydrothiolation of Allenes 3284 2.10. Hydroalxoxylation of Alkenes and 1,3-Dienes 3286 2.11. Hydroamination of Alkenes and 1,3-Dienes 3287 2.12. Hydrothiolation of Conjugated Olefins 3289 3. Activation of Carbonyl/Imine Groups and Alcohols 3289 3.1. Condensation Reactions 3289 3.2. Addition Reactions 3291 3.3. Aldol Reactions 3294 3.4. Hydroand Carbosilylation Reactions 3295 3.5. Nucleophilic Substitution Reactions of Alcohols 3297 4. Gold-Catalyzed C-H Bond Functionalization 3297 4.1. Csp3-H Bond Functionalization 3298 4.2. Csp2-H Bond Functionalization 3299 4.3. Csp-H Bond Functionalization 3304 5. Gold-Catalyzed Selective Reductions 3305 5.1. Catalytic Hydrogenation of Alkenes 3306 5.2. Selective Reductions of R, -Unsaturated Carbonyl Groups and 1,3-Dienes 3306

Alternative synthetic methods through new developments in catalysis by gold.

The challenge of predicting the melting point of ionic liquids is outlined. A descriptor modelling approach for two separate sets of ionic liquids is presented. In each case, the cations and the anions are modelled separately, using quantitative structure-property relationships. Both models include constitutional, topological and geometric descriptors as well as quantum mechanical ones. This approach gives access to (nxm) ionic liquids using only (n+m) calculations. The protocol is tested and validated for predicting the melting points of two sets, comprised of 22 and 62 imidazolium-based ionic liquids, respectively. Good correlations and predictions are obtained in both cases. Within the data set selected (only monopositive and mononegative ions are studied, and so total charge was not a factor), the degree of sphericity is the most important variable for the anion, while for the cation the main descriptors pertained to three radial distribution functions that describe three different sections in the cation. These characterise the ionic interactions, the symmetry-breaking region, and the length of the side chains.

Anion and Cation Effects on Imidazolium Salt Melting Points: A Descriptor Modelling Study

Highly efficient liquid-phase oxidation of primary alcohols to aldehydes with oxygen catalysed by Ru-Co oxide.

The liquid-phase oxidation of a series of saturated and unsaturated non-allylic alcohols to aldehydes with oxygen or air catalysed by tetra-n-propylammonium perruthenate (TPAP, represented as [(n-Pr)4N]RuO4) at 80–110 °C is shown to proceed with selectivities of 72–91% at 55–80% alcohol conversion. The unsaturated alcohols, such as 9-decenol, 9-octadecenol and β-citronellol, give the corresponding unsaturated aldehydes without competing double bond attack. The time course of oxidation indicates a complex reaction mechanism. The results on oxidation of a test alcohol, t-Bu(Ph)CHOH, suggest that one-electron processes do not play an important role in the TPAP-catalysed aerobic oxidation of alcohols.

Oxidation of primary alcohols to aldehydes with oxygen catalysed by tetra-n-propylammonium perruthenate

Scandium trifluoromethaneslfonate, an efficient catalyst for the intermolecular carbonyl-ene reaction and the intramolecular cyclisation of citronellal

The invention relates to the preparation of ceramides by a two step process involving conversion of a 2-hydroximino-3-oxo-alkanoate into a 2-alkanoylamido-3-oxo-alkanoate intermediate by acylation of the oxime and reduction of the oxime ester group to an amido group, followed by reduction of the keto and ester group of the intermediate to the 1,3 diol of the ceramide. The oxime acylation and the first reduction may be carried out consecutively or simultaneously. The first reduction is preferably a catalytic hydrogenation and the second reduction is preferably a borohydride reduction. The invention further relates to novel 2-alkanoylamido-3-oxo-alkanoates and 2-alkanoyloximino-3-oxo-alkanoates which are useful as intermediates for conversion into ceramides.

Paul Nicholas Davey

Papers

Anion and Cation Effects on Imidazolium Salt Melting Points: A Descriptor Modelling Study

Highly efficient liquid-phase oxidation of primary alcohols to aldehydes with oxygen catalysed by Ru-Co oxide.

Oxidation of primary alcohols to aldehydes with oxygen catalysed by tetra-n-propylammonium perruthenate

Scandium trifluoromethaneslfonate, an efficient catalyst for the intermolecular carbonyl-ene reaction and the intramolecular cyclisation of citronellal

Process for the preparation of ceramides